U.S. patent number 4,496,650 [Application Number 06/571,628] was granted by the patent office on 1985-01-29 for silver halide color photographic light-sensitive material.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Tsumoru Hirano, Makoto Umemoto, Morio Yagihara.
United States Patent |
4,496,650 |
Yagihara , et al. |
January 29, 1985 |
Silver halide color photographic light-sensitive material
Abstract
A silver halide color photographic light-sensitive material
comprised of a support having thereon a silver halide emulsion
layer containing a cyan color image forming polymer coupler latex
is disclosed. The cyan color image forming polymer coupler latex is
comprised of at least one repeating unit capable of forming a dye
upon coupling with an oxidation product of an aromatic primary
amine developing agent represented by the general formula (Ia) and
at least one repeating unit represented by the general formula
(II): ##STR1## the substituents within the general formulae are
disclosed within the specification. The cyan color image forming
polymer coupler latex has excellent color forming properties and
the silver halide color photographic light-sensitive material which
contains the latex provides a photograph in which the occurrence of
color stain due to light is substantially prevented. A method of
forming a color image using the silver halide color photographic
light-sensitive material is also described.
Inventors: |
Yagihara; Morio (Kanagawa,
JP), Hirano; Tsumoru (Kanagawa, JP),
Umemoto; Makoto (Kanagawa, JP) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JP)
|
Family
ID: |
11611428 |
Appl.
No.: |
06/571,628 |
Filed: |
January 17, 1984 |
Foreign Application Priority Data
|
|
|
|
|
Jan 17, 1983 [JP] |
|
|
58-5446 |
|
Current U.S.
Class: |
430/381; 430/384;
430/385; 430/505; 430/512; 430/548; 430/552; 430/553; 430/558;
430/931; 548/257 |
Current CPC
Class: |
G03C
7/3275 (20130101); Y10S 430/132 (20130101) |
Current International
Class: |
G03C
7/327 (20060101); G03C 007/16 (); G03C
007/26 () |
Field of
Search: |
;430/381,512,548,552,553,558,505,931,384,385 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Brown; J. Travis
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak and
Seas
Claims
What is claimed is:
1. A silver halide color photographic light-sensitive material
comprising a support having thereon a silver halide emulsion layer
containing a cyan color image forming polymer coupler latex which
comprises at least one repeating unit capable of forming a dye upon
coupling with an oxidation product of an aromatic primary amine
developing agent represented by the general formula (Ia) described
below and at least one repeating unit represented by the general
formula (II) described below: ##STR11## wherein R.sub.1 represents
a hydrogen atom, a lower alkyl group containing from 1 to 4 carbon
atoms or a chlorine atom; and Q.sub.a represents a cyan coupler
moiety-containing group capable of forming a dye upon coupling with
an oxidized aromatic primary amine developing agent, ##STR12##
wherein R.sub.2 represents a hydrogen atom, a lower alkyl group
containing from 1 to 4 carbon atoms or a chlorine atom; A
represents --O-- or --NH--; and Z represents ##STR13## wherein
R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7, which may be the
same or different, each represents a hydrogen atom, an alkyl group,
an alkenyl group, an alkoxy group, a halogen atom, a carboxy group,
a hydroxy group, a nitro group, an aryl group, an acyloxy group, an
aryloxy group, an alkylthio group, an arylthio group, a mono- or
dialkylamino group, an acylamino group, a sulfonamido group or a
5-membered or 6-membered heterocyclic group containing an oxygen
atom or a nitrogen atom, or R.sub.6 and R.sub.7 may be bonded to
each other to form a 5-membered or 6-membered aromatic ring
consisting of carbon atoms, and A may be bonded to any of the
phenol ring and the benzotriazole ring of Z.
2. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the repeating unit represented by the
general formula (Ia) is a repeating unit represented by the general
formula (I) described below: ##STR14## wherein R.sub.1 represents a
hydrogen atom, a lower alkyl group containing from 1 to 4 carbon
atoms or a chlorine atom; and Q represents a cyan coupler residue
capable of forming a dye upon coupling with an oxidized aromatic
primary amine developing agent.
3. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the cyan coupler residue represented by
Q is a cyan color forming phenol type or naphthol type coupler
residue.
4. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the cyan coupler residue represented by
Q is a phenol type residue represented by the following general
formula (III), a phenol type residue represented by the following
general formula (IV) or a naphthol type residue represented by the
following general formula (V): ##STR15## wherein R.sub.8 represents
a hydrogen atom or a lower alkyl group having from 1 to 4 carbon
atoms; A.sub.1 bonds to the NH group in the general formula (I) and
represents an unsubstituted or substituted alkylene group having
from 1 to 10 carbon atoms, an unsubstituted or substituted
aralkylene group having from 7 to 22 carbon atoms, a ##STR16##
group in which p is an integer of from 1 to 10, or an unsubstituted
or substituted phenylene group, where the alkylene group and an
alkylene moiety in the aralkylene group may be a straight chain or
a branched chain; R.sub.9 represents a hydrogen atom or a lower
alkyl group having from 1 to 5 carbon atoms; R.sub.10 represents an
unsubstituted or substituted alkyl group, an unsubstituted or
substituted phenyl group or an unsubstituted or substituted
phenylamino group; X represents a halogen atom; Y represents a
hydrogen atom, a halogen atom or a substituted alkoxy group; m
represents 0 or 1; and n represents 0 or 1.
5. A silver halide color photographic light-sensitive material as
claimed in claim 4, wherein the substituent for the substituted
alkylene group, the substituted aralkylene group or the substituted
phenylene group represented by A.sub.1 is an aryl group, a nitro
group, a hydroxy group, a cyano group, a sulfo group, an alkoxy
group, an aryloxy group, an acyloxy group, an acylamino group, a
sulfonamido group, a sulfamoyl group, a halogen atom, a carboxy
group, a carbamoyl group, an alkoxycarbonyl group or a sulfonyl
group.
6. A silver halide color photographic light-sensitive material as
claimed in claim 4, wherein the substituent for the substituted
alkoxy group represented by Y is an aryl group, a nitro group, a
hydroxy group, a cyano group, a sulfo group, an alkoxy group, an
aryloxy group, an acyloxy group, an acylamino group, an
alkylsulfonamido group, an alkylsulfamoyl group, a halogen atom, a
carboxy group, an alkylcarbamoyl group, an alkoxycarbonyl group, an
alkylsulfonyl group or an alkylthio group.
7. A silver halide color photographic light-sensitive material as
claimed in claim 4, wherein the substituent for the substituted
alkyl group or the substituted phenyl group represented by R.sub.10
is a fluorine atom.
8. A silver halide color photographic light-sensitive material as
claimed in claim 4, wherein the substituent for the substituted
phenylamino group represented by R.sub.10 in a nitro group, a cyano
group, a sulfonamido group, a sulfamoyl group, a halogen atom, a
carbamoyl group or a sulfonyl group.
9. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the cyan color image forming polymer
coupler latex further comprises at least one repeating unit derived
from a non-color forming ethylenically unsaturated monomer.
10. A silver halide color photographic light-sensitive material as
claimed in claim 9, wherein the non-color forming ethylenically
unsaturated monomer is acrylic acid, .alpha.-chloroacrylic acid or
an .alpha.-alkylacrylic acid.
11. A silver halide color photographic light-sensitive material as
claimed in claim 9, wherein the non-color forming ethylenically
unsaturated monomer is an ester derived from acrylic acid, an
.alpha.-chloroacrylic acid or an .alpha.-alkylacrylic acid.
12. A silver halide color photographic light-sensitive material as
claimed in claim 9, wherein the non-color forming ethylenically
unsaturated monomer is an amide derived from acrylic acid, an
.alpha.-chloroacrylic acid or an .alpha.-alkylacrylic acid.
13. A silver halide color photographic light-sensitive material as
claimed in claim 9, wherein the non-color forming ethylenically
unsaturated monomer is a vinyl ester, acrylonitrile,
methacrylonitrile, an aromatic vinyl compound, itaconic acid,
citraconic acid, crotonic acid, vinylidene chloride, a vinyl alkyl
ether, an ester of maleic acid, N-vinyl-2-pyrrolidone,
N-vinylpyridine, 2-vinylpyridine or 4-vinylpyridine.
14. A silver halide color photographic light-sensitive material as
claimed in claim 9, wherein the non-color forming ethylenically
unsaturated monomer is an ester of acrylic acid, an ester of
methacrylic acid, an amide of acrylic acid, an amide of methacrylic
acid or an ester of maleic acid.
15. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the cyan color image forming polymer
coupler latex is a latex prepared by emulsion polymerization of
monomers comprising at least one monomer corresponding to the
repeating unit represented by the general formula (I) and at least
one monomer corresponding to the repeating unit represented by the
general formula (II).
16. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the cyan color image forming polymer
coupler latex is a latex prepared by dissolving an oleophilic
polymer coupler obtained by polymerization of monomers comprising
at least one monomer corresponding to the repeating unit
represented by the general formula (I) and at least one monomer
corresponding to the repeating unit represented by the general
formula (II) in an organic solvent and then dispersing the solution
in a latex form in an aqueous gelatin solution.
17. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the proportion of the color forming
portion corresponding to the general formula (I) in the polymer
coupler latex is from 5% to 80% by weight.
18. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the proportion of the color forming
portion corresponding to the general formula (I) in the polymer
coupler latex is from 20% to 70% by weight.
19. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the proportion of the portion
corresponding to the general formula (II) in the polymer coupler
latex is from 5% to 90% by weight.
20. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the proportion of the portion
corresponding to the general formula (II) in the polymer coupler
latex is from 10% to 70% by weight.
21. A silver halide color photographic light-sensitive material as
claimed in claim 2, wherein the proportion of the portion
corresponding to the general formula (II) is from 30% to 200% by
mole based on the proportion of the color forming portion
corresponding to the general formula (I).
22. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the gram number of the polymer coupler
containing 1 mole of coupler monomer is from 250 to 4,000.
23. A silver halide color photographic light-sensitive material as
claimed in claim 1, wherein the silver halide emulsion layer
containing a cyan color image forming polymer coupler latex is a
red-sensitive silver halide emulsion layer.
24. A silver halide color photographic light-sensitive material as
claimed in claim 23, wherein the photographic light-sensitive
material further comprises a blue-sensitive silver halide emulsion
layer containing a yellow color image forming coupler and a
green-sensitive silver halide emulsion layer containing a magenta
color image forming coupler.
25. A method of forming a color image comprising imagewise exposing
a silver halide color photographic light-sensitive material
comprising a support having thereon a silver halide emulsion layer
containing a cyan color image forming polymer coupler latex which
comprises at least one repeating unit capable of forming a dye upon
coupling with an oxidation product of an aromatic primary amine
developing agent represented by the general formula (Ia) described
below and at least one repeating unit represented by the general
formula (II) described below: ##STR17## wherein R.sub.1 represents
a hydrogen atom, a lower alkyl group containing from 1 to 4 carbon
atoms or a chlorine atom; and Q.sub.a represents a cyan coupler
moiety-containing group capable of forming a dye upon coupling with
an oxidized aromatic primary amine developing agent, ##STR18##
wherein R.sub.2 represents a hydrogen atom, a lower alkyl group
containing from 1 to 4 carbon atoms or a chlorine atom; A
represents --O-- or --NH--; and Z represents ##STR19## wherein
R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7, which may be the
same or different, each represents a hydrogen atom, an alkyl group,
an alkenyl group, an alkoxy group, a halogen atom, a carboxy group,
a hydroxy group, a nitro group, an aryl group, an acyloxy group, an
aryloxy group, an alkylthio group, an arylthio group, a mono- or
dialkylamino group, an acylamino group, a sulfonamido group or a
5-membered or 6-membered heterocyclic group containing an oxygen
atom or a nitrogen atom, or R.sub.6 and R.sub.7 may be bonded to
each other to form a 5-membered or 6-membered aromatic ring
consisting of carbon atoms; and A may be bonded to any of the
phenol ring and the benzotriazole ring of Z, developing the exposed
material using an alkaline aqueous solution containing an aromatic
primary amine developing agent.
Description
FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic
light-sensitive material containing a novel cyan color image
forming polymer coupler latex capable of coupling with an oxidation
product of an aromatic primary amine developing agent.
BACKGROUND OF THE INVENTION
It is well known that upon the color development of a silver halide
photographic light-sensitive material, after exposure, an oxidized
aromatic primary amine developing agent can be reacted with a dye
forming coupler to obtain a color image.
It is also known that, for the color development of a silver halide
color photographic material, an oxidized aromatic primary amine
developing agent can be reacted with a coupler to form a dye such
as an indophenol, an indoaniline, an indamine, an azomethine, a
phenoxazine, a phenazine, and the like, thus forming a color image.
In this procedure, the subtractive color process is ordinarily used
for color reproduction, and silver halide emulsions which are
selectively sensitive to blue, green and red lights, and yellow,
magenta and cyan color image formers, which are respectively the
complementary colors of blue, green and red, are employed. For
example, a coupler of the acylacetanilide or benzoylmethane type is
used for forming a yellow color image; a coupler of the pyrazolone,
pyrazolobenzimidazole, cyanoacetophenone or indazolone type is
generally used for forming a magenta color image; and a coupler of
the phenol type, such as a phenol and a naphthol, is generally used
for forming a cyan color image.
It is also required in a multilayer color photographic
light-sensitive material that each coupler is fixed in a layer
separated from each other in order to reduce color mixing and
improve color reproduction. Many methods for rendering a coupler
diffusion-resistant are known. One method is to introduce a long
chain aliphatic group into a coupler molecule in order to prevent
diffusion. Couplers according to such a method require a step of
addition to an aqueous gelatin solution by solubilizing in alkali,
or a step of dispersing in an aqueous gelatin solution by
dissolving in an organic solvent having a high boiling point, since
the couplers are immiscible with an aqueous gelatin solution. Such
color couplers may cause crystal formation in a photographic
emulsion. Furthermore, when using an organic solvent having a high
boiling point, a large amount of gelatin must be employed since the
organic solvent having a high boiling point makes an emulsion layer
soft. Consequently, this increases the thickness of the material
even though it is desirable to reduce the thickness of the emulsion
layer.
Another method for rendering a coupler diffusion-resistant is to
utilize a polymer coupler latex obtained by polymerization of a
monomeric coupler. An example of a method for adding a polymer
coupler in a latex form to a hydrophilic colloid composition is a
method in which a latex prepared by an emulsion polymerization
method is directly added to a gelatino silver halide emulsion and a
method in which an oleophilic polymer coupler obtained by
polymerization of a monomeric coupler is dispersed in a latex form
in an aqueous gelatin solution. Some examples of the former
emulsion polymerization methods include an emulsion polymerization
method in an aqueous gelatin phase as described in U.S. Pat. No.
3,370,952 and an emulsion polymerization method in water as
described in U.S. Pat. No. 4,080,211. An example of the latter
method in which an oleophilic polymer coupler is dispersed in a
latex form is described in U.S. Pat. No. 3,451,820.
The addition of cyan polymer couplers in a latex form to a gelatino
silver halide emulsion layer is known as described in West German
Pat. No. 2,725,591, U.S. Pat. Nos. 3,926,436 and 3,767,412 and
Research Disclosure, No. 21728 (1982), in addition to the
above-described patents.
The method of adding a polymer coupler in a latex form to a
hydrophilic colloid composition has many advantages in comparison
with other methods. First, the strength of the film formed is not
deteriorated, because the hydrophobic substance is in a latex form.
Second, since the latex can contain coupler monomers in a high
concentration, it is easy to incorporate couplers in a high
concentration into a photographic emulsion, and the crystallization
of couplers in the emulsion layer is eliminated. Third, since the
increase of viscosity is small, it is possible to reduce the
thickness of the emulsion layer which results in the improvement in
sharpness. Fourth, color mixing is prevented, since a polymer
coupler is completely immobilized.
However, these polymer coupler latexes have unsolved problems as
well as many excellent features such as those described above. In
particular, the problem of a cyan polymer coupler latex is color
stain which occurs upon irradiation of light to color photographic
material containing the cyan polymer coupler latex (hereinafter
referred to as light stain).
Since a color photographic material contains many organic compounds
which include a coupler as a representative example, these organic
compounds are decomposed to form various kinds of colored
substances when the color photographic material is irradiated with
light. The colored substances are the origin of the light stain,
particularly in non-image areas or areas of low optical
density.
Many techniques for preventing the occurrence of light stain have
been known. For example, a method is known in which a
2-(2'-hydroxyphenyl)benzotriazole compound is incorporated into a
photographic silver halide emulsion layer to prevent the occurrence
of light stain as described in U.S. Pat. No. 3,253,921.
However, this method is not always sufficient because the effect on
preventing light stain decreases somewhat when the
2-(2'-hydroxyphenyl)benzotriazole compound is added in a large
amount or the color forming property of the coupler is reduced.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a novel
cyan color image forming polymer coupler latex which provides a
lower degree of light stain in a color photograph after development
processing than in conventional methods.
Another object of the present invention is to provide a novel cyan
color image forming polymer coupler latex which has an excellent
color forming property.
A further object of the present invention is to provide a method of
forming a cyan color image by development of a silver halide
emulsion in the presence of a novel cyan color image forming
polymer coupler latex.
A still further object of the present invention is to provide a
silver halide color photographic light-sensitive material
containing a novel cyan color image forming polymer coupler latex,
and a photographic processing method or an image forming method for
using the material.
Other objects of the present invention will be apparent from the
following detailed description and examples.
As a result of extensive investigations, it has now been found that
these objects of the present invention are accomplished by the use
of a cyan color image forming polymer coupler latex which comprises
(1) at least one repeating unit of a cyan coupler corresponding to
the following general formula (Ia): ##STR2## wherein R.sub.1
represents a hydrogen atom, a lower alkyl group containing from 1
to 4 carbon atoms or a chlorine atom; and Q.sub.a represents a cyan
coupler moiety-containing group capable of forming a dye upon
coupling with an oxidized aromatic primary amine developing agent,
and (2) at least one repeating unit of a monomer corresponding to
the following general formula (II): ##STR3## wherein R.sub.2
represents a hydrogen atom, a lower alkyl group containing from 1
to 4 carbon atoms or a chlorine atom; A represents --O-- or --NH--;
and Z represents ##STR4## wherein R.sub.3, R.sub.4, R.sub.5,
R.sub.6 and R.sub.7, which may be the same or different, each
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkoxy group, a halogen atom, a carboxy group, a hydroxy group, a
nitro group, an aryl group, an acyloxy group, an aryloxy group, an
alkylthio group, an arylthio group, a mono- or dialkylamino group,
an acylamino group, a sulfonamido group or a 5-membered or
6-membered heterocyclic group containing an oxygen atom or a
nitrogen atom, or R.sub.6 and R.sub.7 may be bonded each other to
form a 5-membered or 6-membered aromatic ring consisting of carbon
atoms, and A may be bonded to any of the phenol ring and the
benzotriazole ring of Z.
More specifically, the objects of the present invention are
accomplished by a silver halide color photographic light-sensitive
material comprising a support having thereon at least one silver
halide emulsion layer containing the above-described cyan color
image forming polymer coupler latex.
DETAILED DESCRIPTION OF THE INVENTION
The repeating unit of a cyan coupler represented by the general
formula (Ia) is preferably a repeating unit of a cyan coupler
corresponding to the following general formula (I): ##STR5##
wherein R.sub.1 represents a hydrogen atom, a lower alkyl group
containing from 1 to 4 carbon atoms or a chlorine atom; and Q
represents a cyan coupler residue capable of forming a dye upon
coupling with an oxidized aromatic primary amine developing
agent.
In more detail, preferred cyan coupler residue for Q which forms a
cyan color image upon coupling with an oxidized aromatic primary
amine developing agent in the cyan color image forming polymer
coupler latex according to the present invention includes a phenol
type residue represented by the general formula (III) or (IV)
described below and a naphthol type residue represented by the
general formula (V) described below. ##STR6## In the above
formulae, R.sub.8 represents a hydrogen atom or a lower alkyl group
having from 1 to 4 carbon atoms; A.sub.1 bonds to the NH group in
the general formula (I) and represents an unsubstituted or
substituted alkylene group having from 1 to 10 carbon atoms, an
unsubstituted or substituted aralkylene group having from 7 to 22
carbon atoms, a ##STR7## group in which p is an integer of from 1
to 10 (preferably from 1 to 4), or an unsubstituted or substituted
phenylene group, where the alkylene group and an alkylene moiety in
the aralkylene group may be straight chain or branched chain.
Examples of the alkylene group for A.sub.1 include a methylene
group, a methylmethylene group, a dimethylmethylene group, a
dimethylene group, a trimethylene group, a tetramethylene group, a
pentamethylene group, a hexamethylene group, a decylmethylene
group, etc. Examples of the aralkylene group for A.sub.1 includes a
benzylidene group, etc. Examples of the phenylene group for A.sub.1
include a p-phenylene group, an m-phenylene group, a
methylphenylene group, etc. R.sub.9 represents a hydrogen atom or a
lower alkyl group having from 1 to 5 carbon atoms (for example, a
methyl group, an ethyl group, a tert-butyl group, etc.). R.sub.10
represents an unsubstituted or substituted alkyl group, an
unsubstituted or substituted phenyl group or an unsubstituted or
substituted phenylamino group. X represents a halogen atom (for
example, a fluorine atom, a chlorine atom, a bromine atom, etc.). Y
represents a hydrogen atom, a halogen atom (for example, a fluorine
atom, a chlorine atom, a bromine atom, etc.) or a substituted
alkoxy group. m represents 0 or 1; and n represents 0 or 1.
Substituents for the alkylene group, the aralkylene group or the
phenylene group represented by A.sub.1 include an aryl group (for
example, a phenyl group, etc.), a nitro group, a hydroxy group, a
cyano group, a sulfo group, an alkoxy group (for example, a methoxy
group, etc.), an aryloxy group (for example, a phenoxy group,
etc.), an acyloxy group (for example, an acetoxy group, etc.), an
acylamino group (for example, an acetylamino group, etc.), a
sulfonamido group (for example, a methanesulfonamido group, etc.),
a sulfamoyl group (for example, a methylsulfamoyl group, etc.), a
halogen atom (for example, a fluorine atom, a chlorine atom, a
bromine atom, etc.), a carboxy group, a carbamoyl group (for
example, a methylcarbamoyl group, etc.), an alkoxycarbonyl group
(for example, a methoxycarbonyl group, etc.), a sulfonyl group (for
example, a methylsulfonyl group, etc.), and the like. When two or
more substituents are present, they may be the same or
different.
Substituents for the substituted alkoxy group represented by Y
include an aryl group (for example, a phenyl group, etc.), a nitro
group, a hydroxy group, a cyano group, a sulfo group, an alkoxy
group (for example, a methoxy group, etc.), an aryloxy group (for
example, a phenoxy group, etc.), an acyloxy group (for example, an
acetoxy group, etc.), an acylamino group (for example, an
acetylamino group, etc.), an alkylsulfonamido group (for example, a
methanesulfonamido group, etc.), an alkylsulfamoyl group (for
example, a methylsulfamoyl group, etc.), a halogen atom (for
example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a
carboxy group, an alkylcarbamoyl group (for example, a
methylcarbamoyl group, etc.), an alkoxycarbonyl group (for example,
a methoxycarbonyl group, etc.), an alkylsulfonyl group (for
example, a methylsulfonyl group, etc.), an alkylthio group (for
example, a .beta.-carboxyethylthio group, etc.), and the like. When
two or more substituents are present, they may be the same or
different.
Substituent for the alkyl group or the phenyl group represented by
R.sub.10 is preferably a fluorine atom. Substituents for the
phenylamino group represented by R.sub.10 include a nitro group, a
cyano group, a sulfonamido group (for example, a methanesulfonamido
group, etc.), a sulfamoyl group (for example, a methylsulfamoyl
group, etc.), a halogen atom (for example, a fluorine atom, a
chlorine atom, a bromine atom, etc.), a carbamoyl group (for
example, a methylcarbamoyl group, etc.), a sulfonyl group (for
example, a methylsulfonyl group, etc.), and the like. When two or
more substituents are present, they may be the same or
different.
Further, the groups represented by R.sub.3, R.sub.4, R.sub.5,
R.sub.6 and R.sub.7 of the 2-(2'-hydroxyphenyl)benzotriazole
compound represented by Z in the repeating unit represented by the
above-described general formula (II) include a hydrogen atom, a
halogen atom (for example, a chlorine atom, a bromine atom, an
iodine atom, a fluorine atom, etc.), a nitro group, a hydroxy
group, an alkyl group (for example, a methyl group, an ethyl group,
an n-propyl group, an isopropyl group, an aminopropyl group, an
n-butyl group, a sec-butyl group, a tert-butyl group, a chlorobutyl
group, an n-amyl group, an isoamyl group, a cyclohexyl group, an
octyl group, etc.), an alkenyl group (for example, a vinyl group,
an allyl group, etc.), an aryl group (for example, a phenyl group,
a 4-methylphenyl group, a 4-ethoxyphenyl group, etc.), an alkoxy
group (for example, a methoxy group, an ethoxy group, a butoxy
group, a methoxyethoxy group, etc.), an acyloxy group (for example,
an acetoxy group, a butyroyloxy group, etc.), an aryloxy group (for
example, a phenoxy group, a 4-methylphenoxy group, etc.), an
alkylthio group (for example, a methylthio group, an ethylthio
group, a benzylthio group, etc.), an arylthio group (for example, a
phenylthio group, a methylphenylthio group, etc.), a mono- or
dialkylamino group (for example, an N-ethylamino group, an
N,N-diethylamino group, etc.), an acylamino group (for example, an
acetylamino group, a benzoylamio group, etc.), a sulfonamido group
(for example, a methanesulfonamido group, a benzenesulfonamido
group, etc.), a carboxy group and a 5-membered or 6-membered
heterocyclic group containing an oxygen atom or a nitrogen atom
(for example, a piperidino group, a morpholino group, a pyrrolidino
group, a piperazino group, etc.), and R.sub.3, R.sub.4, R.sub.5,
R.sub.6 and R.sub.7 may be the same or different. Further, R.sub.6
and R.sub.7 may be bonded to each other to form a 5-membered or
6-membered aromatic ring consisting of carbon atoms. When R.sub.3,
R.sub.4, R.sub.5, R.sub.6 and R.sub.7 represent a substituent
containing an alkyl moiety, an alkenyl moiety or an aryl moiety,
the alkyl moiety has from 1 to 22 carbon atoms, the alkenyl moiety
has from 2 to 22 carbon atoms and the aryl moiety has from 6 to 22
carbon atoms.
The cyan color image forming polymer coupler latex according to the
present invention includes a copolymer wherein one or more
non-color forming ethylenically unsaturated monomers are
copolymerized together with the ethylenically unsaturated monomer
coupler corresponding to the general formula (I) and the
ethylenically unsaturated 2-(2'-hydroxyphenyl)benzotriazole monomer
corresponding to the general formula (II). Examples of the
copolymerizable non-color forming ethylenically unsaturated
monomers include an acrylic acid (for example, acrylic acid, an
.alpha.-chloroacrylic acid, an .alpha.-alkylacrylic acid such as
methacrylic acid, etc.), an ester and an amide derived from an
acrylic acid (for example, acrylamide, methacrylamide,
n-butylacrylamide, t-butylacrylamide, n-octylacrylamide,
diacetoneacrylamide, hydroxymethylacrylamide,
n-butylmethacrylamide, methyl acrylate, ethyl acrylate, n-propyl
acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl
methacrylate, ethyl methacrylate, n-butyl methacrylate,
.beta.-hydroxymethacrylate, etc.), a vinyl ester (for example,
vinyl acetate, vinyl propionate, vinyl laurate, etc.),
acrylonitrile, methacrylonitrile, an aromatic vinyl compound (for
example, styrene and a derivative thereof, for example, vinyl
toluene, divinyl benzene, vinyl acetophenone, sulfostyrene, etc.),
itaconic acid, citraconic acid, crotonic acid, vinylidene chloride,
a vinyl alkyl ether (for example, vinyl ethyl ether, etc.), an
ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- or
4-vinylpyridine, etc.
Of these monomers, an ester of acrylic acid, an ester of
methacrylic acid, an amide of acrylic acid, an amide of methacrylic
acid, an ester of maleic acid are particularly preferred.
Two or more non-color fomring ethylenically unsaturated monomers
described above can be used together. For example, a combination of
methyl acrylate and n-butyl acrylate, methyl acrylate and
diacetoneacrylamide, styrene and n-butyl acrylate, etc., can be
employed.
The ethylenically unsaturated monomer which is used to copolymerize
with the monomer coupler corresponding to the above-described
general formula (I) can be selected so that the copolymer to be
formed possesses good physical properties and/or chemical
properties, for example, solubility, compatibility with a binder
such as gelatin in a photographic colloid composition, flexibility,
heat stability, etc., as well known in the field of polymer color
couplers.
The cyan polymer coupler latex used in the present invention can be
prepared, as described above, by dissolving an oleophilic polymer
coupler obtained by polymerization of a monomer coupler in an
organic solvent and then dispersing the solution in a latex form in
an aqueous gelatin solution, or can be directly prepared by an
emulsion polymerization method. With respect to the method in which
an oleophilic polymer coupler is dispersed in a latex form in an
aqueous gelatin solution, the method as described in U.S. Pat. No.
3,451,820 and with respect to the emulsion polymerization, the
methods as described in U.S. Pat. Nos. 4,080,211 and 3,370,952 can
be employed, respectively.
In the following, general methods for preparing the cyan polymer
coupler latexes are described.
Free radical polymerization of an ethylenically unsaturated solid
monomer is initiated with the addition to the monomer molecule of a
free radical which is formed by thermal decomposition of a chemical
initiator, an action of a reducing agent to an oxidative compound
(a redox initiator) or a physical action, for example, irradiation
of ultraviolet rays or other high energy radiations, high
frequencies, etc.
Examples of the chemical initiators commonly used include a
water-soluble initiator, for example, a persulfate (such as
ammonium persulfate, potassium persulfate, etc.), hydrogen
peroxide, 4,4'-azobis(4-cyanovaleric acid), etc.; and a
water-insoluble initiator, for example, an azobisisobutyronitrile
(such as 2,2'-azobis(2,4-dimethylvaleronitrile,
2,2'-azobisisobutyronitrile, etc.), dimethyl
2,2'-azobisisobutyrate, benzoyl peroxide, chlorobenzoyl peroxide,
and other compounds. Examples of the redox initiators usually used
include hydrogen peroxide-iron (II) salt, potassium
persulfate-potassium hydrogensulfate, cerium salt-alcohol, etc.
Specific examples and functions of the initiators are described in
F. A. Bovey, Emulsion Polymerization, pages 59 to 93 (Interscience
Publishers Inc., New York (1955)).
Solvents which can be used in polymerization of the oleophilic cyan
polymer couplers are preferably those which can usually be admixed
with monomers to be used without limitation, are good solvents for
the oleophilic polymer couplers formed, do not react with
initiators to be used and do not interrupt usual actions in free
radical addition polymerization.
Specific examples of the solvents which can be used include an
aromatic hydrocarbon (for example, benzene, toluene, etc.), a
hydrocarbon (for example, n-hexane, etc.), an alcohol (for example,
methanol, ethanol, isopropanol, n-propanol, tert-butanol, etc.), a
ketone (for example, acetone, methyl ethyl ketone, etc.), a cyclic
ether (for example, tetrahydrofuran, dioxane, etc.), an ester (for
example, ethyl acetate, etc.), a chlorinated hydrocarbon (for
example, methylene chloride, chloroform, etc.), an amide (for
example, dimethylformamide, dimethylacetamide, etc.), a sulfoxide
(for example, dimethyl sulfoxide, etc.), a nitrile (for example,
acetonitrile, etc.), and a mixture thereof.
Further, an organic solvent, which is used for dissolving an
oleophilic polymer coupler in the case where the oleophilic polymer
coupler is dispersed in a latex form in an aqueous gelatin
solution, is removed from the mixture before coating of the
dispersion solution or by vaporization during drying of the
dispersion solution coated. Although the latter is less preferable.
With respect to removing the solvent, a method in which the solvent
is removed by washing a gelatin noodle with water is applied when
the solvent is water-soluble to some extent, or a spray drying
method, a vacuum purging method or a steam purging method can be
employed for removing the solvent.
Examples of the organic solvents which can be removed include, for
example, an ester (for example, a lower alkyl ester, etc.), a lower
alkyl ether, a ketone, a halogenated hydrocarbon (for example,
methylene chloride, trichloroethylene, a fluorinated hydrocarbon,
etc.), an alcohol (for example, an alcohol between n-butyl alcohol
and octyl alcohol, etc.), and a mixture thereof.
Any type of dispersing agent can be used in the dispersion of the
oleophilic polymer coupler. Ionic surface active agents, and
particularly anionic surface active agents, are preferred.
Amphoteric surface active agents such as C-cetyl betaine, an
N-alkylaminopropionate, an N-alkyliminodipropionate, etc., can also
be used.
On the other hand, emulsion polymerization of solid water-insoluble
monomer couplers is usually carried out in an aqueous system or a
water/organic solvent system. Organic solvents which can be used
are preferably those which are substantially inert to solid
water-insoluble monomer couplers to be used, do not interrupt usual
actions in free radical addition polymerization, and have a low
boiling point so as to be capable of being easily removed from an
aqueous reaction medium by distillation during and/or after
polymerization, same as the organic solvents described above.
Preferred examples include a lower alcohol having from 1 to 4
carbon atoms (for example, methanol, ethanol, isopropanol, etc.), a
ketone (for example, acetone, etc.), a chlorinated hydrocarbon (for
example, chloroform, etc.), an aromatic hydrocarbon (for example,
benzene, etc.), a cyclic ether (for example, tetrahydrofuran,
etc.), an ester (for example, ethyl acetate, etc.), a nitrile (for
example, acetonitrile, etc.), and the like.
As an emulsifier which can be used in the emulsion polymerization,
a compound having surface activity is used. Preferred examples
include soap, a sulfonate, a sulfate, a cationic compound, an
amphoteric compound and a high molecular weight protective colloid.
Specific examples and functions of the emulsifiers are described in
Belgische Chemische Industrie, Vol. 28, pages 16 to 20 (1963).
In order to improve the dispersion stability, to improve the color
forming property of a polymer coupler dispersed, to control the
color hue of a dye formed from a polymer coupler and the oxidation
product of an aromatic primary amine developing agent and to
improve the bending property of the emulsion coated, a permanent
solvent, that is, a water-immiscible organic solvent having a high
boiling point (i.e., above 200.degree. C.), may be added in a small
amount. The concentration of the permanent solvent must be at such
a low level that the copolymer is plasticized while it is
maintained in solid particle form. Furthermore, it is desirable to
use the permanent solvent in a relatively low concentration in
order to reduce the thickness of a final emulsion layer as much as
possible to obtain good sharpness.
It is desirable that a proportion of the color forming portion
corresponding to the general formula (I) in the cyan polymer
coupler latex is usually from 5 to 80% by weight. Particularly, a
proportion from 20 to 70% by weight is preferred in view of color
reproducibility, color forming property and stability. Also, it is
desirable that a proportion of the portion corresponding to the
general formula (II) in the cyan polymer coupler latex is usually
from 5 to 90% by weight. Particularly, a proportion from 10 to 70%
by weight is preferred in view of color reproducibility, color
forming property and fastness. Further, it is preferred that the
proportion of the portion corresponding to the general formula (II)
is from 30 to 200% by mole based on the proportion of the color
forming portion corresponding to the general formula (I). In this
case, an equivalent molecular weight, that is, the gram number of
the polymer containing 1 mole of the monomer coupler is from about
250 to 4,000, but it is not limited thereto.
Specific examples of monomer couplers suitable for preparing the
cyan polymer coupler latex according to the present invention are
described in various literature references, for example, U.S. Pat.
Nos. 2,976,294, 3,767,412, 4,080,211 and 4,128,427, Research
Disclosure, Vol. 217, No. 21728, etc.
Representative examples of the monomer couplers corresponding to
the general formula (Ia) which can be used in the present invention
are set forth below, but the present invention is not to be
construed as being limited thereto. ##STR8##
Examples of the 2-(2'-hydroxyphenyl)benzotriazole monomer
corresponding to the general formula (II) are described, for
example, in British Pat. No. 1,346,764, etc. Specific examples
thereof are set forth below, but the present invention is not to be
construed as being limited thereto. ##STR9##
In the following, typical synthesis examples of the cyan polymer
coupler latexes according to the present invention are set
forth.
SYNTHESIS METHOD I
SYNTHESIS EXAMPLE 1
Synthesis of copolymer of
6-methacrylamido-2,4-dichloro-3-methylphenol [Monomer Coupler (1)],
2-(2'-hydroxy-3'-methacrylamido-5'-methylphenyl)benzotriazole
[Monomer (ii)] and methyl acrylate [Oleophilic Polymer Coupler
(I)]
A mixture composed of 30 g of Monomer Coupler (1), 30 g of
2-(2'-hydroxyphenyl)benzotriazole Monomer (ii), 40 g of methyl
acrylate and 500 ml of dioxane was heated to 80.degree. C. with
stirring while introducing nitrogen gas. To the mixture was added
20 ml of a dioxane containing 1.5 g of dimethyl azobisisobutyrate
dissolved to initiate polymerization. After reacting for 5 hours,
the reaction solution was cooled and poured into 3 liters of water.
The solid thus deposited were collected by filtration and
thoroughly washed with water. By drying the solid under a reduced
pressure with heating, 95.2 g of Oleophilic Polymer Coupler (I) was
obtained. It was found that the oleophilic polymer coupler
contained 32.7% of Monomer Coupler (1) in the copolymer synthesized
as the result of chlorine analysis.
A method for dispersing Oleophilic Polymer Coupler (I) in an
aqueous gelatin solution in the form of a latex is described in the
following.
Two solutions (a) and (b) were prepared in the following
manner.
Solution (a): 200 g of a 30% by weight aqueous solution of bone
gelatin (pH of 5.6 at 35.degree. C.) was heated to 38.degree. C.
and to which was added 16 ml of a 10% by weight aqueous solution of
sodium lauryl sulfate.
Solution (b): 20 g of Oleophilic Polymer Coupler (I) described
above was dissolved in 200 ml of ethyl acetate at 38.degree. C.
Solution (b) was put into a mixer with explosion preventing
equipment while stirring at a high speed to which was rapidly added
solution (a). After stirring for 1 minute, the mixer was stopped
and ethyl acetate was removed by distillation under a reduced
pressure. Thus, the oleophilic polymer coupler was dispersed in a
diluted gelatin solution to prepare Polymer Coupler Latex (I').
SYNTHESIS EXAMPLE 2
Synthesis of copolymer of 6-acrylamido-2,4-dichloro-3-methylphenol
[Monomer Coupler (2)],
2-(5'-tert-butyl-2'-hydroxy-3'-methacrylamidophenyl)benzotriazole
[Monomer (v)] and butyl acrylate [Oleophilic Polymer Coupler
(II)]
A mixture composed of 20 g of Monomer Coupler (2), 10 g of
2-(2'-hydroxyphenyl)benzotriazole Monomer (v), 20 g of butyl
acrylate and 250 ml of dioxane was heated to 80.degree. C. with
stirring while introducing nitrogen gas. To the mixture was added
10 ml of dioxane containing 0.5 g of dimethyl azobisisobutyrate
dissolved to initiate polymerization. After reacting for 5 hours,
the reaction solution was cooled and poured into 1.5 liters of
water. The solid thus deposited was collected by filtration and
thoroughly washed with water. By drying the solid under a reduced
pressure with heating, 46.5 g of Oleophilic Polymer Coupler (II)
was obtained. It was found that the oleophilic polymer coupler
contained 40.8% of Monomer Coupler (2) in the copolymer synthesized
as the result of chlorine analysis.
A method for dispersing Oleophilic Polymer Coupler (II) in an
aqueous gelatin solution in the form of a latex is described in the
following.
Two solutions (a) and (b) were prepared in the following
manner.
Solution (a): 200 g of a 30% by weight aqueous solution of bone
gelatin (pH of 5.6 at 35.degree. C.) was heated to 38.degree. C.
and to which was added 16 ml of a 10% by weight aqueous solution of
sodium lauryl sulfate.
Solution (b): 20 g of Oleophilic Polymer Coupler (II) described
above was dissolved in 200 ml of ethyl acetate at 38.degree. C.
Solution (b) was put into a mixer with explosion preventing
equipment while stirring at high speed and to which was rapidly
added solution (a). After stirring for 1 minute, the mixer was
stopped and ethyl acetate was removed by distillation under a
reduced pressure. Thus, the oleophilic polymer coupler was
dispersed in a diluted gelatin solution to prepare Polymer Coupler
Latex (II').
SYNTHESIS EXAMPLE 3
Synthesis of copolymer coupler of
6-(3-methacrylamidopropanamido)-2,4-dichloro-3-methylphenol
[Monomer Coupler (9)],
2-(2'-hydroxyphenyl)-5-methacrylamidobenzotriazole [Monomer (vii)]
and methyl acrylate [Oleophilic Polymer Coupler (III)]
A mixture composed of 20 g of Monomer Coupler (9), 10 g of
2-(2'-hydroxyphenyl)benzotriazole Monomer (vii), 45 g of methyl
acrylate and 400 ml of dioxane was heated to 85.degree. C. with
stirring while introducing nitrogen gas. To the mixture was added
20 ml of dioxane containing 1 g of azobisisobutyronitrile dissolved
to initiate polymerization. After reacting for 4 hours, the
reaction temperature was raised to 100.degree. C. and the mixture
was further reacted for 2 hours. The reaction solution was cooled
and poured into 3 liters of water and the solid thus deposited was
collected by filtration. By drying the solid under a reduced
pressure with heating, 69.8 g of Oleophilic Polymer Coupler (III)
was obtained. It was found that the oleophilic polymer coupler
contained 28.5% of Monomer Coupler (9) in the copolymer synthesized
as the result of chlorine analysis.
A method for dispersing Oleophilic Polymer Coupler (III) in an
aqueous gelatin solution in the form of a latex is described in the
following.
Two solutions (a) and (b) were prepared in the following
manner.
Solution (a): 200 g of a 30% by weight aqueous solution of bone
gelatin (pH of 5.6 at 35.degree. C.) was heated to 38.degree. C.
and to which was added 16 ml of a 10% by weight aqueous solution of
sodium lauryl sulfate.
Solution (b): 20 g of Oleophilic Polymer Coupler (III) described
above was dissolved in 200 ml of ethyl acetate at 38.degree. C.
Solution (b) was put into a mixer with explosion preventing
equipment while stirring at high speed and to which was rapidly
added solution (a). After stirring for 1 minute, the mixer was
stopped and ethyl acetate was removed by distillation under a
reduced pressure. Thus, the oleophilic polymer coupler was
dispersed in a diluted gelatin solution to prepare Polymer Coupler
Latex (III').
SYNTHESIS EXAMPLES 4 TO 25
Using the above-described monomer couplers and the
2-(2'-hydroxyphenyl)benzotriazole monomers, Oleophilic Polymer
Couplers (IV) to (XXV) described below were prepared in the same
manner as described for the copolymers in Synthesis Examples 1 to
3.
__________________________________________________________________________
Oleophilic Polymer Couplers by Synthesis Method I 2-(2'-Hydroxy-
phenyl)-benzo- Monomer Monomer triazole Non-Color*.sup.1 Coupler
Oleophilic Coupler Monomer Forming Monomer Unit in Synthesis
Polymer Amount Amount Amount Polymer Example Coupler Kind (g) Kind
(g) Kind (g) (wt %)
__________________________________________________________________________
4 IV (1) 30 (ii) 20 MA 50 32.1 5 V (1) 30 (ii) 10 MA 60 33.0 6 VI
(1) 30 (v) 20 MA 30 31.8 DAAM 20 7 VII (1) 30 (v) 30 MA 40 31.6 8
VIII (1) 30 (vii) 30 MA 40 32.5 9 IX (2) 30 (ii) 30 MA 40 32.1 10 X
(2) 20 (v) 15 EA 35 28.8 11 XI (6) 20 (v) 20 BA 40 25.0 12 XII (6)
20 (vii) 20 MA 30 35.2 13 XIII (9) 30 (ii) 30 MA 40 32.7 14 XIV (9)
20 (ii) 10 BA 10 51.0 15 XV (11) 20 (ii) 20 MA 40 26.0 16 XVI (12)
20 (ii) 20 MA 35 25.6 MAA 5 17 XVII (12) 20 (ii) 30 BA 34 24.5 18
XVIII (15) 20 (v) 20 BA 27 31.2 19 XIX (15) 30 (v) 10 BA 30 42.8 20
XX (17) 20 (vii) 10 BA 30 33.9 21 XXI (18) 30 (ii) 10 BA 30 43.8 22
XXII (18) 20 (v) 10 EA 30 34.2 23 XXIII (20) 20 (v) 10 BA 30 34.0
24 XXIV (20) 20 (ii) 10 MA 25 34.3 MAA 5 25 XXV (20) 20 (i) 10 BA
30 34.0
__________________________________________________________________________
*.sup.1 MA: Methyl Acrylate EA: Ethyl Acrylate BA: Butyl Acrylate
MAA: Methacrylic Acid DAAM: Diacetoneacrylamide
The amounts of the monomer couplers, the
2-(2'-hydroxyphenyl)benzotriazole monomers and the non-color
forming monomers in the above table indicate amounts used in the
synthesis of the oleophilic polymer couplers.
Dispersion of these oleophilic polymer couplers in the form of a
latex can be carried out in the same manner as described in
Synthesis Examples 1 to 3.
SYNTHESIS METHOD II
SYNTHESIS EXAMPLE 26
Synthesis of copolymer latex of
6-methacrylamido-2,4-dichloro-3-methylphenol [Monomer Coupler (1)],
2-(2'-hydroxy-3'-methacrylamido-5'-methylphenyl)benzotriazole
[Monomer (ii)] and methyl acrylate [Polymer Coupler Latex (A)]
1.5 liters of an aqueous solution containing 4 g of oleyl methyl
tauride dissolved was heated to 85.degree. C. with stirring while
introducing nitrogen gas in a 3 liter flask. To the aqueous
solution was added 40 ml of a 2% aqueous solution of potassium
persulfate and then was added dropwise over a period of 20 minutes
a solution prepared by dissolving with heating 20 g of Monomer
Coupler (1), 20 g of 2-(2'-hydroxyphenyl)benzotriazole Monomer (ii)
and 40 g of methyl acrylate in 500 ml of methanol. After reacting
for 1 hour, 10 ml of a 2% aqueous solution of potassium persulfate
was added. After further reacting for 1 hour, the methanol was
distilled off. The latex thus formed was cooled, pH of which was
adjusted to 6.0 with a 1N sodium hydroxide solution and filtered.
The concentration of the polymer in the latex formed was 5.3% and
it was found that the polymer contained 26.0% of Monomer Coupler
(1) as the result of chlorine analysis.
SYNTHESIS EXAMPLE 27
Synthesis of copolymer latex of
6-acrylamido-2,4-dichloro-3-methylphenyl [Monomer Coupler (2)],
2-(2'-hydroxyphenyl)-5-methacrylamidobenzotriazole [Monomer (vii)]
and methyl acrylate [Polymer Coupler Latex (B)]
600 ml of an aqueous solution containing 3.3 g of oleyl methyl
tauride dissolved was heated to 80.degree. C. with stirring while
introducing nitrogen gas in a 1 liter flask. To the aqueous
solution were added 3 ml of a 2% aqueous solution of potassium
persulfate and 6 g of methyl acrylate. After 1 hour, 20 g of
Monomer Coupler (2), 10 g of 2-(2'-hydroxyphenyl)benzotriazole
Monomer (vii), 30 g of methyl acrylate and 250 ml of methanol were
added and then 20 ml of a 2% aqueous solution of potassium
persulfate was added. After 1 hour, 8 ml of a 2% aqueous solution
of potassium persulfate was added. After further reacting for 1
hour, the methyl acrylate not reacted and the methanol were
distilled off. The latex thus formed was cooled, pH of which was
adjusted to 6.0 with a 1N sodium hydroxide solution and filtered.
The concentration of the polymer in the latex formed was 11.9% and
it was found that the polymer contained 31.2% of Monomer Coupler
(2) as the result of chlorine analysis.
SYNTHESIS EXAMPLES 28 TO 37
Using the above-described monomer couplers, and the
2-(2'-hydroxyphenyl)benzotriazole monomers, Polymer Coupler Latexes
(C) to (L) described below were prepared in the same manner as
described for the copolymer in Synthesis Example 26.
__________________________________________________________________________
Polymer Coupler Latexes by Synthesis Method II 2-(2'-Hydroxy-
phenyl)-benzo- Monomer Monomer triazole Non-Color*.sup.2 Coupler
Polymer Coupler Monomer Forming Monomer Unit in Synthesis Coupler
Amount Amount Amount Polymer Example Latex Kind (g) Kind (g) Kind
(g) (wt. %)
__________________________________________________________________________
28 C (1) 20 (i) 20 BA 30 28.1 29 D (1) 20 (iii) 10 MA 20 34.2 DAAM
10 30 E (2) 20 (ii) 10 MA 20 41.8 31 F (2) 20 (v) 10 BA 15 44.6 32
G (9) 20 (ii) 20 MA 30 29.5 33 H (9) 20 (vi) 10 MA 30 34.0 34 I
(11) 20 (v) 20 EA 30 29.5 35 J (11) 20 (vii) 20 BA 30 28.8 36 K
(12) 20 (ii) 10 MA 20 40.6 37 L (12) 20 (v) 10 MA 15 41.0 MMA 5
__________________________________________________________________________
*.sup.2 MA: Methyl Acrylate EA: Ethyl Acrylate BA: Butyl Acrylate
DAAM: Diacetoneacrylamide MMA: Methyl Methacrylate
The amounts of the monomer couplers, the
2-(2'-hydroxyphenyl)benzotriazole monomers and the non-color
forming monomers in the above table indicate amounts used in the
synthesis of the polymer coupler latexes.
The cyan polymer coupler latexes according to the present invention
can be used individually or as mixtures of two or more thereof.
Tye cyan polymer coupler latexes according to the present invention
can also be used together with a cyan polymer coupler latex, such
as those described in U.S. Pat. No. 4,080,211, West German Pat. No.
2,725,591, U.S. Pat. No. 3,926,436 and Research Disclosure, No.
21728, etc.
Further, a dispersion which is prepared by dispersing a hydrophobic
cyan color forming coupler such as a phenol coupler or a naphthol
coupler, for example, a cyan coupler, as described in U.S. Pat.
Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383,
3,767,411 and 4,004,929, West German Patent Application (OLS) Nos.
2,414,830 and 2,454,329, Japanese Patent Application (OPI) Nos.
59838/73, 26034/76, 5055/73, 146828/76 and 73050/80 (the term "OPI"
as used herein refers to a "published unexamined Japanese patent
application"), etc., in a hydrophilic colloid in a manner as
described, for example, in U.S. Pat. Nos. 2,269,158, 2,272,191,
2,304,940, 2,311,020, 2,322,027, 2,360,289, 2,772,163, 2,801,170,
2,801,171 and 3,619,195, British Pat. No. 1,151,590, West German
Pat. No. 1,143,707, etc., is loaded into the cyan polymer coupler
latex according to the present invention in a manner as described
in Japanese Patent Publication No. 39853/76, etc., and the
resulting latex can be used. The term "load" used herein refers to
the state in which a hydrophobic cyan coupler is incorporated into
the interior of a cyan polymer coupler latex, or a state in which a
hydrophobic cyan coupler is deposited on the surface of a cyan
polymer coupler latex. However, the mechanism by which the load
occurs is not accurately known.
In order to satisfy the characteristics required for the
photographic light-sensitive material, a dispersion which is
prepared by dispersing a development inhibitor releasing (DIR)
coupler as described, for example, in U.S. Pat. Nos. 3,148,062,
3,227,554, 3,733,201, 3,617,291, 3,703,375, 3,615,506, 3,265,506,
3,620,745, 3,632,345, 3,869,291, 3,642,485, 3,770,436 and
3,808,945, British Pat. Nos. 1,201,110 and 1,236,767, etc., in a
hydrophilic colloid in a manner as described in U.S. Pat. Nos.
2,269,158, 2,272,191, 2,304,940, 2,311,020, 2,322,027, 2,360,289,
2,772,163, 2,801,170, 2,801,171 and 3,619,195, British Pat. No.
1,151,590, West German Pat. No. 1,143,707, etc., is loaded into the
cyan polymer coupler latex according to the present invention in a
manner as described in Japanese Patent Publication No.
39853/76.
Futthermore, the cyan polymer coupler latex according to the
present invention can be used together with a DIR compound as
described, for example, in West German Patent Application (OLS)
Nos. 2,529,350, 2,448,063 and 2,610,546, U.S. Pat. Nos. 3,928,041,
3,958,993, 3,961,959, 4,049,455, 4,052,213, 3,379,529, 3,043,690,
3,364,022, 3,297,445 and 3,287,129.
Moreover, the cyan polymer coupler latex according to the present
invention can be used in combination with a competing coupler as
described, for example, in U.S. Pat. Nos. 3,876,428, 3,580,722,
2,998,314, 2,808,329, 2,742,832 and 2,689,793, etc., a stain
preventing agent as described, for example, in U.S. Pat. Nos.
2,336,327, 2,728,659, 2,336,327, 2,403,721, 2,701,197 and
3,700,453, etc., a dye image stabilizing agent as described, for
example, in British Pat. No. 1,326,889, U.S. Pat. Nos. 3,432,300,
3,698,909, 3,574,627, 3,573,050 and 3,764,337, etc., or the
like.
The color photographic light-sensitive material produced according
to the present invention can also contain conventionally well known
coupler(s) other than a cyan color forming coupler. A
non-diffusible coupler which contains a hydrophobic group, called a
ballast group, in the molecule thereof is preferred as a coupler. A
coupler can have either a 4-equivalent or a 2-equivalent property
with respect to the silver ion. In addition, a colored coupler
providing a color correction effect, or a coupler which releases a
development inhibitor upon a development can also be present
therein. Furthermore, a coupler which provides a colorless product
upon coupling can be employed.
A known open chain ketomethylene type coupler can be used as a
yellow color forming coupler. Of these couplers, benzoylacetanilide
type and pivaloylacetanilide type compounds are especially
effective. Specific examples of yellow color forming couplers which
can be employed are described, for example, in U.S. Pat. Nos.
2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072
and 3,891,445, West German Pat. No. 1,547,868, West German Patent
Application (OLS) Nos. 2,219,917, 2,261,361 and 2,414,006, British
Pat. No. 1,425,020, Japanese Patent Publication No. 10783/76,
Japanese Patent Application (OPI) Nos. 26133/72, 73147/73,
102636/76, 6341/75, 123342/75, 130442/75, 21827/76 and 87650/75,
etc.
A 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a
cyanoacetylcumaron coupler, an open chain acylacetonitrile coupler,
etc., can be used as a magenta color forming coupler. Specific
examples of magenta color forming couplers which can be employed
are described, for example, in U.S. Pat. Nos. 2,600,788, 2,983,608,
3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319,
3,582,322, 3,615,506, 3,834,908 and 3,891,445, West German Pat. No.
1,810,464, West German Patent Application (OLS) Nos. 2,408,665,
2,417,945, 2,418,959 and 2,424,467, Japanese Patent Publication No.
6031/65, Japanese Patent Application (OPI) Nos. 20826/76, 58922/77,
129538/74, 74027/74, 159336/75, 42121/77, 74028/74, 60233/75,
26541/76 and 55122/78, etc.
Two or more kinds of the couplers described above can be
incorporated into the same layer, or the same coupler compound can
also be present in two or more layers.
A known method, for example, the method described in U.S. Pat. No.
2,322,027, can be used in order to incorporate the couplers
described above into a silver halide emulsion layer. The coupler is
dispersed in a hydrophilic colloid and then mixed with a silver
halide emulsion. For example, the coupler may be dissolved in an
organic solvent having a high boiling point, for example, a
phthalic acid alkyl ester (e.g., dibutyl phthalate, dioctyl
phthalate, etc.), a phosphoric acid ester (e.g., diphenyl
phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl
phosphate, etc.), a citric acid ester (e.g., tributyl
acetylcitrate, etc.), a benzoic acid ester (e.g., octyl benzoate,
etc.), an alkylamide (e.g., diethyl laurylamide, etc.), a fatty
acid ester (e.g., dibutoxyethyl succinate, dioctyl azelate, etc.),
a trimesic acid ester (e.g., tributyl trimesate, etc.), etc., or in
an organic solvent having a low boiling point of from about
30.degree. to about 150.degree. C., for example, a lower alkyl
acetate (e.g., ethyl acetate, butyl acetate, etc.), ethyl
propionate, sec-butyl alcohol, methyl isobutyl ketone,
.beta.-ethoxyethyl acetate, methyl Cellosolve acetate, etc., and
then the solution is dispersed in a hydrophilic colloid. The
abovedescribed organic solvent having a high boiling point and the
above-described organic solvent having a low boiling point may be
used as mixture, if desired.
Furthermore, the dispersing method using a polymeric material as
described in Japanese Patent Publication No. 39853/76 and Japanese
Patent Application (OPI) No. 59943/76 can also be used.
When a coupler having an acid group, such as a carboxylic acid
group, a sulfonic acid group, etc., is used, it can be incorporated
in a hydrophilic colloid as an alkaline aqueous solution
thereof.
The silver halide emulsions which can be used in the present
invention are those wherein silver chloride, silver bromide, or a
mixed silver halide such as silver chlorobromide, silver
iodobromide, or silver chloroiodobromide is finely dispersed in a
hydrophilic polymer such as gelatin. The silver halide can be
chosen depending on the intended use of the photographic
light-sensitive material from dispersions having a uniform grain
size or those having a wide grain size distribution or from
dispersions having an average grain size of from about 0.1 micron
to 3 microns. These silver halide emulsions can be prepared, for
example, by a single jet method, by a double jet method or a
controlled double jet method, or by a ripening method such as an
ammonia method, a neutral method, or an acid method. Also, these
silver halide emulsions can be subjected to chemical sensitization
such as a sulfur sensitization, a gold sensitization, a reduction
sensitization, etc., and can contain a speed increasing agent such
as a polyoxyethylene compound, an onium compound, etc. Further, a
silver halide emulsion of the type wherein latent images are
predominantly formed on the surface of the grains or of the type
where latent images are predominantly formed inside the grains can
be used in the present invention. Also, two or more kinds of silver
halide photographic emulsions prepared separately and then mixed
can be employed.
Suitable examples of a hydrophilic high molecular weight substance
composed of the photographic light-sensitive layer of the present
invention include a protein such as gelatin, etc., a high molecular
weight non-electrolyte such as polyvinyl alcohol, polyvinyl
pyrrolidone, polyacrylamide, etc., an acidic high molecular weight
substance such as an alginate, a polyacrylic acid salt, etc., a
high molecular weight ampholite such as a polyacrylamide treated
with the Hoffman rearrangement reaction, a copolymer of acrylic
acid and N-vinylimidazole, etc., a cross-linkable polymer such as
those described in U.S. Pat. No. 4,215,195, and the like.
Furthermore, a dispersion of a hydrophobic high molecular weight
substance such as a latex of polybutyl acrylate, etc., can be
included in the continuous phase of such a hydrophilic high
molecular weight substance.
The silver halide emulsion used in the present invention can be
chemically sensitized, as noted above, using conventional methods.
Examples of suitable chemical sensitizers include, for example, a
gold compound such as a chloroaurate and gold trichloride, as
described in U.S. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 and
2,597,915; a salt of a noble metal, such as platinum, palladium,
iridium, rhodium and ruthenium, as described in U.S. Pat. Nos.
2,448,060, 2,540,086, 2,566,245, 2,566,263 and 2,598,079; a sulfur
compound capable of forming silver sulfide by reacting with a
silver salt, such as those described in U.S. Pat. Nos. 1,574,944,
2,410,689, 3,189,458 and 3,501,313; a stannous salt, an amine, and
other reducing compounds such as those described in U.S. Pat. Nos.
2,487,850, 2,518,698, 2,521,925, 2,521,926, 2,694,637, 2,983,610
and 3,201,254 and the like.
Various compounds can be added to the photographic emulsions used
in the present invention in order to prevent a reduction of the
sensitivity or a formation of fog during preparation, storage or
processing. A wide variety of such compounds are known, such as a
heterocyclic compound, mercury-containing compound, a mercapto
compound or a metal salt, including
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 3-methylbenzothiazole
and 1-phenyl-5-mercaptotetrazole, etc. Other examples of such
compounds which can be used are described, for example, in U.S.
Pat. Nos. 1,758,576, 2,110,178, 2,131,038, 2,173,628, 2,697,040,
2,304,962, 2,324,123, 2,349,198, 2,444,605-8, 2,566,245, 2,694,716,
2,697,099, 2,708,162, 2,728,663-5, 2,476,536, 2,824,001, 2,843,491,
2,886,437, 3,052,544, 3,137,577, 3,220,839, 3,226,231, 3,236,652,
3,251,691, 3,252,799, 3,287,135, 3,326,681, 3,420,668 and
3,622,339, British Pat. Nos. 893,428, 403,789, 1,173,609 and
1,200,188, as well as in K. Mees, The Theory of the Photographic
Process, 3rd Ed. (1966) and the literature references cited
therein.
The photographic emulsion used in the present invention can also
contain a surface active agent individually or as a mixture
thereof. These surface active agents are commonly used as a coating
aid. However, in some cases they are used for the purposes of
emulsion dispersion, sensitization, static prevention, adhesion
prevention, etc.
The surface active agents can be classified into various groups, as
follows: a natural surface active agent such as saponin, etc.; a
nonionic surface active agent such as an alkylene oxide, a glycerol
and a glycidol, etc.; a cationic surface active agent such as a
higher alkylamine, a quaternary ammonium salt, a heterocyclic
compound such as pyridine and the like, a phosphoniums, a
sulfoniums, etc.; an anionic surface active agent containing an
acid group such as a carboxylic acid group, a sulfonic acid group,
a phosphoric acid group, a sulfuric acid ester group, a phosphoric
acid ester group, etc.; an amphoteric surface active agent such as
an amino acid, an aminosulfonic acid, an aminoalcohol sulfuric acid
ester, an aminoalcohol phosphoric acid ester, etc. Some examples of
those surface active agents which can be used are described in U.S.
Pat. Nos. 2,271,623, 2,240,472, 2,288,226, 2,739,891, 3,068,101,
3,158,484, 3,201,253, 3,210,191, 3,294,540, 3,415,649, 3,441,413,
3,442,654, 3,475,174, 3,545,974, West German Patent Application
(OLS) No. 1,942,665, British Pat. Nos. 1,077,317 and 1,198,450, as
well as Ryohei Oda et al., Kaimenkasseizai no Gosei to Sono Oyo
(Synthesis and Application of Surface Active Agents), Maki Shoten
(1964), A. W. Perry, Surface Active Agents, Interscience
Publications, Inc. (1958) and J. P. Sisley, Encyclopedia of Surface
Active Agents, Vol. II, Chemical Publishing Co. (1964), etc.
The photographic emulsion can be spectrally sensitized, or
supersensitized, using a cyanine-type dye, such as a cyanine,
merocyanine, carbocyanine, etc., individually, in combination, or
in combination with a styryl dye.
These spectral sensitization techniques are well known, and are
described, for example, in U.S. Pat. Nos. 2,688,545, 2,912,329,
3,397,060, 3,615,635 and 3,628,964, British Pat. Nos. 1,195,302,
1,242,588 and 1,293,862, West German Patent Application (OLS) Nos.
2,030,326 and 2,121,780, Japanese Patent Publication Nos. 4936/68
and 14030/69, etc. The sensitizers can be selected as desired
depending on the wavelength range, sensitivity, etc., due to the
purpose and use of the photographic light-sensitive material to be
sensitized.
The hydrophilic colloid layer, and in particular, a gelatin layer
in the photographic light-sensitive material used in the present
invention, can be hardened using various kinds of cross-linking
agents. For instance, an inorganic compound such as a chromium
salt, a zirconium salt, etc., or an aldehyde type cross-linking
agent such as mucochloric acid, or 2-phenoxy-3-chloromalealdehydic
acid as described in Japanese Patent Publication No. 1872/71 can be
effectively used in the present invention. However, a non-aldehyde
type cross-linking agent such as a compond having plural epoxy
rings as described in Japanese Patent Publication No. 7133/59, a
poly(1-aziridinyl) compound as described in Japanese Patent
Publication No. 8790/62, an active halogen compound as described in
U.S. Pat. Nos. 3,362,827 and 3,325,287, a vinyl sulfone compound as
described in U.S. Pat. Nos. 2,994,611 and 3,582,322, Belgian Pat.
No. 686,440, etc., are particularly suitable for use in the
photographic light-sensitive material of the present invention.
The silver halide photographic emulsion according to the present
invention is suitably applied to a support. Illustrative supports
include a rigid material such as glass, a metal and a ceramic, and
a flexible material and the type of support chosen depends on the
end-use objects. Typical examples of flexible supports include a
cellulose nitrate film, a cellulose acetate film, a polyvinyl
acetal film, a polystyrene film, a polyethylene terephthalate film,
a polycarbonate film and a laminate thereof, a baryta coated paper,
a paper coated with an .alpha.-olefin polymer, such as
polyethylene, polypropylene and an ethylene-butene copolymer, a
plastic film having a roughened surface as described in Japanese
Patent Publication No. 19068/72, and the like. Depending upon the
end-use objects of the photographic light-sensitive material, the
support can be transparent, colored by adding a dye or pigment,
opaque by adding, for example, titanium white, or light-shielding
by adding, for example, carbon black.
The layer of the photographic light-sensitive material can be
coated on a support using various coating methods, including a dip
coating method, an air-knife coating method, a curtain coating
method, an extrusion coating method using a hopper as described in
U.S. Pat. No. 2,681,294. Also, two or more layers can be coated
simultaneously, using methods as described in U.S. Pat. Nos.
2,761,791, 3,508,947, 2,941,898, 3,526,528, etc.
In practice of the present invention, a known fade-preventing agent
can be used. A color image stabilizing agent can be used alone
individually or in combination two or more thereof. Examples of
known fade-preventing agents include a hydroquinone derivative, a
gallic acid derivative, a p-alkoxyphenol, a p-oxyphenol derivative
or a biphenol, etc.
Specific examples of hydroquinone derivatives are described in U.S.
Pat. Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713,
2,728,659, 2,732,300, 2,735,765, 2,710,801 and 2,816,028, British
Pat. No. 1,363,921, etc. Specific examples of gallic acid
derivatives are described in U.S. Pat. Nos. 3,457,079 and
3,069,262, etc. Specific examples of p-alkoxyphenols are described
in U.S. Pat. Nos. 2,735,765 and 3,698,909, Japanese Patent
Publication Nos. 20977/74 and 6623/77, etc. Specific examples of
p-oxyphenol derivatives are described in U.S. Pat. Nos. 3,432,300,
3,573,050, 3,574,627 and 3,764,337, Japanese Patent Application
(OPI) Nos. 35633/77, 147434/77 and 152225/77, etc. Specific
examples of bisphenols are described in U.S. Pat. No.
3,700,455.
The photographic light-sensitive material of the present invention
may contain an ultraviolet light absorbing agent in a hydrophilic
colloid layer. For example, a benzotriazole compound substituted
with an aryl group (for example, those described in U.S. Pat. No.
3,533,794), a 4-thiazolidone compound (for example, those described
in U.S. Pat. Nos. 3,314,794 and 3,352,681), a benzophenone compound
(for example, those described in Japanese Patent Application (OPI)
No. 2784/71), a cinnamic ester compound (for example, those
described in U.S. Pat. Nos. 3,705,805 and 3,707,375), and a
benzoxazole compound (for example, those described in U.S. Pat. No.
3,499,762) can be employed. An ultraviolet light absorbing coupler
(for example, .alpha.-naphthol type cyan dye forming coupler) and
an ultraviolet light absorbing polymer can also be employed. These
ultraviolet light absorbing agents may be mordanted to a specific
layer. Also, these ultraviolet light absorbing agents may be
contained within the layer containing the cyan polymer coupler of
the present invention.
The present invention is applicable to not only the so-called
multilayer type photographic light-sensitive material comprising a
support having super-imposed thereon emulsion layers, each of which
is sensitive to radiation of a substantially different wavelength
region and forms color images of a substantially different hue, but
also the so-called mixed packet type photographic light-sensitive
material comprising a support having coated thereon a layer
containing packets which are sensitive to radiation of
substantially different wavelength regions and form color images of
a substantially different hue. The present invention can be applied
to a color negative film, a color positive film, a color reversal
film, a color printing paper, a color reversal printing paper, and
the like.
The color photographic light-sensitive material of the present
invention is, after exposure, subjected to a development processing
to form dye images. Development processing includes basically a
color development step, a bleaching step and a fixing step. Each
step can be carried out individually or two or more steps can be
combined as one step where a processing solution having two or more
functions is used. Also, each step can be separated into two or
more steps. The development processing can further include a
pre-hardening step, a neutralization step, a first development
(black-and-white development) step, a stabilizing step, a water
washing step, and the like, if desired. The temperature of
processing can be varied depending on the photographic
light-sensitive material, the processing method, and the like. In
general, the processing steps are carried out at a temperature from
18.degree. C. to 60.degree. C. These steps need not necessarily be
conducted at the same temperature.
A color developer solution is an alkaline solution having a pH of
more than 8, preferably from 9 to 12, and containing, as a
developing agent, a compound whose oxidation product is capable of
forming a colored compound when reacted with a color forming agent,
i.e., a color coupler. The developing agent described above include
a compound capable of developing an exposed silver halide and
having a primary amino group on an aromatic ring, and a precursor
which forms such compound. Typical examples of preferred developing
agents are, for example, 4-amino-N,N-diethylaniline,
3-methyl-4-amino-N,N-diethylaniline,
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethylaniline,
4-amino-N,N-dimethylaniline, 4-amino-3-methoxy-N,N-diethylaniline,
4-amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline,
4-amino-3-methoxy-N-ethyl-N-.beta.-methoxyethylaniline,
4-amino-3-.beta.-methanesulfonamidoethyl-N,N-diethylaniline, and a
salt thereof (for example, a sulfate, a hydrochloride, a sulfite, a
p-toluene sulfonate, and the like). Other developing agents such as
those described in U.S. Pat. Nos. 2,193,015 and 2,592,364, Japanese
Patent Application (OPI) No. 64933/73, L. F. A. Mason, Photographic
Processing Chemistry, pages 226-229, Focal Press, London (1966), T.
H. James, The Theory of the Photographic Process, 4th Edition,
pages 315-320, Macmillan, New York (1977), etc., can be used.
Further, an aminophenol as described in T. H. James, The Theory of
the Photographic Process, 4th Edition, pages 311-315, etc., can be
used. Also, a 3-pyrazolidone developing agent can be used together
with these developing agents.
The color developing solution can optionally contain various
additives. Typical examples of such additives include an alkaline
agent (for example, an alkali metal or ammonium hydroxide,
carbonate or phosphate, etc.); a pH adjusting agent or buffer (for
example, a weak acid such as acetic acid, boric acid, etc., a weak
base, or salt thereof, etc.); a developing accelerator (for
example, various pyridinium compounds or cationic compounds such as
those described in U.S. Pat. Nos. 2,648,604 and 3,671,247;
potassium nitrate; sodium nitrate; a condensation product of
polyethylene glycol, and a derivative thereof such as those
described in U.S. Pat. Nos. 2,533,990, 2,577,127 and 2,950,970; a
nonionic compound such as a polythioether represented by those
described in British Pat. Nos. 1,020,033 and 1,020,032; a polymeric
compound having a sulfite ester group such as those described in
U.S. Pat. No. 3,068,097; an organic amine such as pyridine and
ethanolamine; benzyl alcohol; a hydrazine and the like); an
antifogging agent (for example, an alkali metal bromide; an alkali
metal iodide; a nitrobenzimidazole such as those described in U.S.
Pat. Nos. 2,496,940 and 2,656,271; mercaptobenzimidazole;
5-methylbenzotriazole; 1-phenyl-5-mercaptotetrazole; a compound for
use in rapid processing such as those described in U.S. Pat. Nos.
3,113,864, 3,342,596, 3,295,976, 3,615,522 and 3,597,199; a
thiosulfonyl compound such as those described in British Pat. No.
972,211; a phenazine-N-oxide such as those described in Japanese
Patent Publication No. 41675/71; fog inhibiting agents described in
Kagaku Shashin Binran (Manual of Scientific Photography), Vol. II,
pages 29-47, and the like); a stain or sludge preventing agent such
as those described in U.S. Pat. Nos. 3,161,513 and 3,161,514, and
British Pat. Nos. 1,030,442, 1,144,481 and 1,251,558; an
interlayer-effect accelerator disclosed in U.S. Pat. No. 3,536,487;
a preservative (for example, a sulfite, a bisulfite, hydroxyamine
hydrochloride, formsulfite, an alkanolaminesulfite adduct, etc.)
and the like.
The color photographic light-sensitive material of the present
invention can be treated with various solutions prior to color
development.
In the case of color reversal films, treatment with a first
development solution is also carried out prior to the color
development. As the first development solution, an alkaline aqueous
solution containing at least one developing agent, such as
hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p-aminophenol and
the like can be employed. The solution can also contain an
inorganic salt such as sodium sulfate, etc.; a pH adjusting agent
or buffer such as borax, boric acid, sodium hydroxide and sodium
carbonate, etc.; a development fog preventing agent such as an
alkali metal halide (such as potassium bromide, etc.), and the
like.
The additives illustrated above and the amounts thereof employed
are well known in the color processing field.
After color development, the color photographic materials are
usually bleached and fixed. The process can be effected in a blix
bath which combines the bleaching and fixing steps. Various known
compounds can be used as a bleaching agent, for example, a
ferricyanide, a dichromate; a water-soluble iron (III) salt, a
water-soluble cobalt (III) salt; a water-soluble copper (II) salt;
a water-soluble quinone; a nitrosophenol, a complex salt of a
polyvalent cation such as iron (III), cobalt (III), copper (II),
etc., and an organic acid, for example, a metal complex of an
aminopolycarboxylic acid such as ethylenediaminetetraacetic acid,
nitrilotriacetic acid, iminodiacetic acid,
N-hydroxyethylethylenediaminetriacetic acid, etc., malonic acid,
tartaric acid, malic acid, diglycolic acid and dithioglycolic acid,
and a copper complex salt of 2,6-dipicolinic acid; a peracid such
as an alkylperacid, a persulfate, a permanganate and hydrogen
peroxide; hypochlorite; chlorine; bromine; bleaching powder; and
the like. These can be suitably used, individually or in
combination. To the bleaching solution, a bleaching accelerator
such as those described in U.S. Pat. Nos. 3,042,520 and 3,241,966,
Japanese Patent Publication Nos. 8506/70 and 8836/70 and various
other additives can be added.
Any known fixing solution can be used for fixing the photographic
material of the present invention. That is, ammonium, sodium or
potassium thiosulfate can be used as a fixing agent at a
concentration of about 50 to about 200 g/liter. Fixing solution can
further contain a stabilizer such as a sulfite and a metabisulfite;
a hardener such as potassium alum; a pH buffer such as an acetate
and borate, and the like. The fixing solution generally has a pH of
more than 3 or less.
Bleaching bath, fixing bath and blixing bath as described, for
example, in U.S. Pat. No. 3,582,322, Japanese Patent Application
(OPI) No. 101934/73, West German Pat. No. 1,051,117, etc., can also
be employed.
The present invention will be explained in greater detail with
reference to the following examples, but the present invention
should not be construed as being limited thereto.
EXAMPLE 1
On a paper support both surfaces of which were laminated with
polyethylene were coated on a first layer (undermost layer) to a
sixth layer (uppermost layer) as shown below in order to prepare a
color photographic light-sensitive material which is designated
Sample 1.
In Table 1 below, a coating amount is set forth in mg/m.sup.2.
TABLE 1 ______________________________________ Sixth Layer: Gelatin
(1,600 mg/m.sup.2) (protective layer) Fifth Layer: Silver
chlorobromide (red-sensitive emulsion layer) (silver bromide: 50
mol % silver: 300 mg/m.sup.2) Cyan coupler (*1) (400 mg/m.sup.2)
Coupler solvent (*2) (300 mg/m.sup.2) Ultraviolet light (200
mg/m.sup.2) absorbing agent (*3) - Gelatin (500 mg/m.sup.2) Fourth
Layer: Ultraviolet light (600 mg/m.sup.2) (ultraviolet light
absorbing agent (*3) absorbing layer) Ultraviolet light (300
mg/m.sup.2) absorbing agent solvent (*2) Gelatin (800 mg/m.sup.2)
Third Layer: Silver chlorobromide (green-sensitive emulsion layer)
(silver bromide: 70 mol % silver: (500 mg/m.sup.2) Magenta coupler
(*4) (400 mg/m.sup.2) Color-fading (200 mg/m.sup.2) preventing
agent (*5) Coupler solvent (*6) (400 mg/m.sup.2) Gelatin (700
mg/m.sup.2) Second Layer: Gelatin (1,000 mg/m.sup.2) (intermediate
layer) First Layer: Silver chlorobromide (blue-sensitive emulsion
layer) (silver bromide: 80 mol % silver: (400 mg/m.sup.2) Yellow
coupler (*7) (500 mg/m.sup.2) Coupler solvent (*2) (400 mg/m.sup.2)
Gelatin (700 mg/m.sup.2) Support: Paper support both surfaces of
which were laminated with polyethylene
______________________________________ (*1) Cyan coupler:
2[(2,4-Di-tert-pentylphenoxy)-butanamido4,6-dichloro-5-methyl-phenol
(*2) Solvent: Trinonyl phosphate (*3) Ultraviolet light absorbing
agent: 2(2-Hydroxy-3-sec-butyl-5-tert-butyl)benzotriazole (*4)
Magenta coupler:
1(2,4,6-Trichlorophenyl)3-(2-chloro-5-tetradecanamido)anilino-2-pyrazolin
5-one (*5) Color fading preventing agent:
2,5Di-tert-hexylhydroquinone (*6) Coupler solvent: Tricresyl
phosphate (*7) Yellow coupler:
pivaloyl-(2,4-dioxo-5,5dimethyloxazolidin-3-yl)-2-chloro-5-[(2,4-di-
tertpentylphenoxy)-butanamido]acetanilide
Sample 2 was prepared in the same manner as described in Sample 1
except that the ultraviolet light absorbing agent in the
red-sensitive layer of Sample 1 was eliminated. Also, Samples 3 and
4 were prepared in the same manner as described in Samples 1 and 2
except that the cyan coupler solvent in Samples 1 and 2 was
eliminated, respectively. Further, Samples 5 and 6 were prepared in
the same manner as described in Samples 3 and 4 except that 700
mg/m.sup.2 of the oleophilic cyan polymer coupler having the
structure shown below was used in the form of a latex in place of
the cyan coupler in Samples 3 and 4, respectively. ##STR10##
Furthermore, Samples 7, 8, 9, 10, 11, 12, 13 and 14 were prepared
in the same manner as described in Sample 6 except that 700
mg/m.sup.2 of Oleophilic Cyan Polymer Couplers (I), (IV), (V),
(VII), (VIII), (IX) and (XIII) in the form of a latex and 700
mg/m.sup.2 (in an amount of the polymer coupler) of Polymer Coupler
Latex (A) according to the present invention were used respectively
in place of the oleophilic cyan polymer coupler in Sample 6.
Each sample was exposed to red light through a continuous wedge and
subjected to color development processing in the following
manner.
______________________________________ Temperature Processing Step
(.degree.C.) Time ______________________________________ Color
Development 33 3 min 30 sec Bleach-Fixing 33 1 min 30 sec Washing
with Water 30 3 min Drying
______________________________________
The processing solutions used in the color development processing
had the following compositions:
______________________________________ Color Developing Solution
Benzyl Alcohol 15 ml Sodium Sulfite 5 g Potassium Bromide 0.4 g
Hydroxylamine Sulfate 2 g
4-(N--Ethyl-N--.beta.-methanesulfonamido)- 2 g 2-methylaniline
Sesquisulfate Sodium Carbonate (monohydrate) 30 g Water to make
1,000 ml (pH 10.1) Bleach-Fixing Solution Ferric
Ethylenediaminetetraacetate 45 g Sodium Sulfite 10 g Ammonium
Thiosulfate (70% aq. soln.) 160 ml Tetrasodium
Ethylenediaminetetra- 5 g acetate Water to make 1,000 ml (pH 6.8)
______________________________________
The color density in each sample after development processing was
measured. The fog, gamma and maximum density in each sample are
shown in Table 2 below.
TABLE 2 ______________________________________ Maximum Sample Fog
Gamma Density Remarks ______________________________________ 7 0.12
3.18 3.15 Present Invention 8 0.11 3.21 3.22 " 9 0.11 3.24 3.25 "
10 0.12 3.20 3.18 " 11 0.11 3.15 3.15 " 12 0.12 3.19 3.17 " 13 0.12
3.17 3.16 " 14 0.12 3.11 3.10 " 1 0:11 3.12 3.06 Comparison 2 0.12
3.15 3.10 " 3 0.11 3.22 3.20 " 4 0.11 3.23 3.23 " 5 0.11 2.94 2.73
" 6 0.12 2.99 2.81 " ______________________________________
As is apparent from the results shown in Table 2 above, Samples 7
to 14 containing the oleophilic cyan polymer coupler latexes
according to the present invention have excellent color forming
properties.
Further, Samples 1 to 14 after development processing were
maintained in an almost dry atmosphere at 80.degree. C. for 3 weeks
and then the density reduction rates of the cyan color image in the
areas where the initial densities were 1.0 (D 1.0) and 2.0 (D 2.0)
were measured. The results thus obtained are shown in Table 3
below.
TABLE 3 ______________________________________ 80.degree. C., 3
Weeks D 1.0 D 2.0 Sample (%) (%) Remarks
______________________________________ 7 19 20 Present Invention 8
26 27 " 9 34 32 " 10 20 18 " 11 18 19 " 12 18 20 " 13 19 19 " 14 23
20 " 1 55 53 Comparison 2 53 54 " 3 52 50 " 4 54 50 " 5 41 39 " 6
38 42 " ______________________________________
It is apparent from the results shown in Table 3 above that the
samples containing the oleophilic cyan polymer latex according to
the present invention have excellent heat fastness.
Moreover, Samples 1 to 14 after development processing were
subjected to the color fading test in a xenon light color fading
testing equipment (1.3.times.10.sup.5 lux) for 192 hours. Then, the
density reduction rates of the cyan color image in the areas where
the initial densities were 1.0 (D 1.0) and 2.0 (D 2.0) and the
coloring in the white area (light stain: yellow color density) were
measured. The results thus obtained are shown in Table 4 below.
TABLE 4 ______________________________________ Xenon (1.3 .times.
10.sup.5 lux) for 192 Hrs. D 1.0 D 2.0 Yellow Density Sample (%)
(%) in White Area Remarks ______________________________________ 7
55 52 0.28 Present Invention 8 57 53 0.32 Present Invention 9 53 55
0.37 Present Invention 10 54 57 0.27 Present Invention 11 50 54
0.28 Present Invention 12 55 56 0.28 Present Invention 13 50 57
0.27 Present Invention 14 55 54 0.29 Present Invention 1 47 39 0.40
Comparison 2 50 43 0.55 " 3 57 55 0.47 " 4 60 56 0.56 " 5 53 50
0.50 " 6 57 52 0.58 " ______________________________________
It is apparent from the results shown in Table 4 above that in the
samples containing the oleophilic cyan polymer coupler latex
according to the present invention the occurrence of light stain is
remarkably prevented.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *